WO2000066639A1

WO2000066639A1 - Propylene copolymer and molded object obtained by molding the copolymer

Info

Publication number: WO2000066639A1
Application number: PCT/JP2000/002738
Authority: WO
Inventors: Shinichi Yukimasa; Masahiko Endo; Masato Kijima; Takayuki Nakagawa
Original assignee: Idemitsu Petrochemical Co., Ltd.
Priority date: 1999-04-28
Filing date: 2000-04-26
Publication date: 2000-11-09
Also published as: DE60008219D1; DE60008219T2; US6423782B1; EP1162213A4; EP1162213B1; JP2000313777A; EP1162213A1

Abstract

A propylene copolymer which has an excellent balance among transparency, ordinary-temperature impact resistance, low-temperature impact resistance, flexibility, and blocking resistance. The propylene copolymer comprises: [A] 50 to 90 wt.% propylene/ethylene copolymer in which (1) the ethylene content (α) is 0.2 to 10 wt.%, (2) the content of components (Wp) eluting in the temperature range of from (Tp-5) °C to (Tp+5) °C in temperature-rising fractional chromatography is 20 wt.% or higher, provided that Tp (°C) is the main elution peak temperature in the chromatogram, and (3) the content of components (W0) eluting in the temperature range not higher than 0 °C determined from that chromatogram and α satisfy the realtionship W0 ≤ (3+2α) / 4; and [B] 10 to 50 wt.% propylene/ethylene copolymer having an ethylene content of 10 to 25 wt.%.

Description

Akira Itoda Propylene-based copolymer and molded product obtained by molding the copolymer

The present invention relates to a propylene-based copolymer and a molded product obtained by molding the copolymer. More specifically, the present invention relates to propylene having a good balance of transparency, room-temperature impact properties, low-temperature impact properties, flexibility and blocking properties. The present invention relates to a system copolymer and a molded product obtained by molding the copolymer. Background art

In the field of polypropylene-based resins, high-rigidity materials are being actively developed, while the development of softer and softer materials is also attracting attention. As a soft material, a material which is excellent in flexibility, maintains high transparency, and has excellent impact resistance is desired.

In response to these demands, propylene homopolymers, random copolymers of propylene and ethylene, or propylene homopolymers or copolymers in the first stage are produced, and propylene and other polymers are produced in the second stage. Propylene block copolymers obtained by random copolymerization of α-olefins with α-olefins have been proposed. However, a propylene homopolymer is inferior in flexibility and impact resistance, and a random copolymer of propylene and ethylene is excellent in transparency but inferior in flexibility and impact resistance. In addition, conventional pyrene block copolymers have excellent impact resistance because the crystalline phase and amorphous phase exhibit a sea-island structure, but the transparency is reduced due to the difference in the refractive index of each component. There was a disadvantage that it was inferior in flexibility. As described above, the conventional technology is not suitable for transparency, room temperature impact, low temperature impact, flexibility and blockage. At present, no polypropylene polymer with an excellent balance of durability has been obtained.

An object of the present invention is to provide a propylene-based copolymer having an excellent balance of transparency, room-temperature impact, low-temperature impact, flexibility and blocking property, and a molded article obtained by molding the copolymer. I do. Disclosure of the invention

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a solid catalyst component comprising magnesium, titanium, a halogen atom and a specific electron-donating compound, an organic aluminum compound and a specific organic silicon compound. Propylene copolymer obtained by multi-stage polymerization of propylene copolymer in which the comonomer content is changed at high temperature in gas phase polymerization in the presence of a catalyst system consisting of The inventors have found that the balance of impact, flexibility and blocking properties is excellent, and based on this, the present invention has been completed. That is, the present invention provides the following propylene-based copolymer and a molded article obtained by molding the copolymer.

1. Propylene satisfy (1) to (3) below - ethylene copolymer [A] propylene Ren one ethylene copolymer 50-90 ^_0/0 and having an ethylene content of 10 to 25 weight ⁰ / o [ B] the propylene-based copolymer comprising 10 to 50 weight _{^0/0 using.}

(1) Ethylene content as measured by ¹³ C-NMR) is 0.2 to 10% by weight

(2) Assuming that the main elution peak temperature of the temperature-increased fractionation chromatograph is Tp CC), when the component (Wp) eluted in the temperature range of (Tp-5) to (Tp + 5) t is 20 wt% or more, is there

(3) Elution is performed in the temperature range of 0 or less in the temperature separation chromatography. Satisfies the relationship of component amount (WO) and _α force WO ≤ (3 + 2α) / 4

2. The propylene copolymer according to 1 above, wherein the propylene copolymer is obtained by a propylene block copolymerization method in which propylene and ethylene are copolymerized in multiple stages.

3. Propylene one ethylene copolymer satisfying (1) to (3) below [Alpha] 50 to 85 weight ⁰ / o and an ethylene content of propylene Ren one ethylene copolymer is 10 to 25 weight ^_0/0 [ Β] The propylene-based copolymer according to 1 or 2 above, comprising 15 to 50% by weight.

(1) The ethylene content (c) measured by ¹³ C-NMR is 0.5 to 9% by weight

(2) Assuming that the main elution peak temperature of the temperature rising fractionation chromatograph is Tp CC), the amount of eluted component (Wp) in the temperature range of (Tp-5) to (Tp + 5) is 20% by weight or more.

(3) The amount of component eluted (W0) and α in the temperature range of 0¾ or less in the temperature rising fractionation chromatograph satisfy the relationship of W0 ≤ (3 + 2α) 4

4. The component amount of [Β] in the propylene-based copolymer (3) (% by weight) and the tensile modulus (ΤΜ) (unit: MPa) satisfy any of the above 1 to 3 in which the following relationship is satisfied. The propylene-based copolymer according to the above.

TM <2 X 10 ⁵ X (β) " ^L?

5. The propylene block copolymerization method described in 2 above comprises: (A) a solid catalyst component obtained by contacting and reacting a magnesium compound, a titanium compound, and an electron-donating compound; (B) an organoaluminum compound; ) The following general formula (I)

S i R ¹ ₂ (OR ² ) ₂

(Wherein, R ¹ is a branched chain hydrocarbon group having 1 to 20 carbon atoms, or a saturated cyclic carbon group. R ² represents a straight-chain hydrocarbon group having 1 to 4 carbon atoms or a branched-chain hydrocarbon group; These may be the same or different from each other. 5. The propylene-based copolymer according to any one of the above items 2 to 4, which is a production method in which propylene and ethylene are multistage polymerized in the presence of a catalyst comprising an organic silicon compound represented by the formula:

6. The propylene block copolymerization method in the above 2) is carried out at a temperature of 12 to 15 in the presence of (A) a magnesium compound, a titanium compound, an electron-donating compound and, if necessary, a silicon compound. After letting

A solid catalyst component obtained by washing with an inert solvent at a temperature of 10 or more and 15 or less, (B) an organoaluminum compound, and, if necessary, (C) a catalyst comprising an electron-donating compound as the third component. 5. The propylene-based copolymer according to any one of the above items 2 to 4, which is a production method in which propylene and ethylene are subjected to multistage polymerization in the presence.

7. A molded article comprising the propylene-based copolymer according to any one of 1 to 4 above. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the propylene-based copolymer [I] of the present invention and the molded article [II] obtained by molding the copolymer will be described in detail.

[I] Propylene copolymer

Propylene copolymer of the present invention, the following (1) to (3) flop propylene one ethylene copolymer satisfying [A] 50 to 90 weight ^_0/0 and an ethylene content of 10 to 25 weight ⁰ /. [B] is a propylene-based copolymer comprising 10 to 50% by weight.

(1) Ethylene content measured by ¹³ C-NMR) is 0.2 to 10 Weight percent

(2) Assuming that the main elution peak temperature of the temperature rising fractionation chromatograph is Tp (), the amount of eluted component (Wp) in the temperature range of (Τρ-5) to (Tp + 5) t is 20% by weight or more. is there

(3) Satisfies the relationship between the amount of components eluted (W0) and α force W0 ≤ (3 + 2α) 4 in the following temperature range of the temperature-separation chromatography

The propylene-based copolymer of the present invention satisfies the requirements described above, and the molded product obtained by molding the copolymer has an excellent balance of transparency, room-temperature impact properties, low-temperature impact properties, flexibility and blocking properties. For example, a film obtained by molding has a tensile modulus of 100 OMPa or less, a haze of 15%, and more preferably a tensile modulus of 8 O OMP a to 10 O OMPa and a haze of 10% to 1%. %. In addition, it has the advantages of excellent cold shock resistance and low temperature shock resistance, low stickiness, and excellent blocking properties.

Propylene copolymer of the present invention, propylene one ethylene copolymer [A] 50 to 90 weight ^_0/0 and propylene one ethylene copolymer [B] consists of 10 to 5 0 wt%. Preferably, it comprises [A] 50 to 85% by weight and [B] 15 to 50% by weight. If [B] is less than 1% by weight, flexibility and impact resistance are lacking. On the other hand, if the amount of the component [B] exceeds 5% by weight, the film blocking property and the powder fluidity deteriorate.

Propylene copolymer of the present invention, the following (1) to flop propylene one ethylene copolymer satisfying (3) [A] 50~ 85 weight ^_0/0 and an ethylene content of 10 to 25 weight ⁰ /. The propylene-ethylene copolymer [B] is more preferably 15 to 50% by weight.

(1) The ethylene content (α) measured by ¹³ C-NMR is 0.5 to 9% by weight

(2) The main elution peak temperature of the temperature-separated chromatograph was defined as Tp CC). When (Tp-5) ^< t: The amount of eluted component (Wp) in the temperature range of (Tp + 5) is 20% by weight or more.

(3) Satisfies the relationship between the amount of components eluted (W0) and _α force W0 ≤ (3 + 2α) Ζ4 in the temperature range of 0 or less in the temperature rising fractionation chromatograph

Further, the propylene-ethylene copolymer [Β] in the present invention needs to have an ethylene content of 10 to 25 weight ⁰ / ο. Preferably, 15-25 weight ⁰ /. It is. If the ethylene content of [Β] is less than 10% by weight, the impact resistance is undesirably reduced. If it exceeds 25% by weight, the transparency is reduced.

The propylene copolymer of the present invention may be a so-called propylene block copolymer obtained by a propylene block copolymerization method in which propylene and ethylene are copolymerized in multiple stages.

Next, each component will be described.

[1] Propylene-ethylene copolymer [Α]

The propylene-ethylene copolymer [Α] in the present invention satisfies the above (1) to (3). That is,

(1) ¹³ C-ethylene content determined by NMR (ct) is from 0.2 to 10 weight ^_0/0, preferably from 0.5 to 9 weight ^_0/0, more preferably 1 to 5% by weight. If the ethylene content ( _α ) is less than 0.2, the effect of improving heat sealability cannot be expected. Also made to those 1 0 weight ⁰ / o by weight, the rigidity of the film is not satisfactory. The ethylene content ( _α ) is determined by the measurement method using ¹³ C-NMR described in Example “Method for evaluating resin characteristics”.

(2) Assuming that the main elution peak temperature of the temperature rising fractionation chromatograph is Tp CC), the amount of eluted component (Wp) in the temperature range of (Tp-5) to (Tp + 5) ° C is 20% by weight or more. Is

Preferably, 20≤Wp _N and (80—15 a) ≤Wp

And more preferably,

30≤Wp and (90— 1 2a) ≤Wp

It is.

When Wp is less than 20% by weight, the tail of the main elution peak extends greatly to the high temperature side and Z or low temperature side, and the low temperature side component is a sticky film formed. However, components on the high-temperature side are not preferred because they cause insufficient heat sealing properties and increase the dependence of transparency on molding conditions. “Tp CC)” refers to the temperature at which the elution amount shows a peak in the elution curve obtained by the measurement method of temperature-separation chromatography described in “Resin Characteristic Evaluation Method” in Example. W ρ is determined from the obtained elution curve.

(3) Satisfies the relationship between the amount of eluted components (W0) and ^; W0 ≤ (3 + 2a) / 4 in the following temperature range of the fractionated chromatograph. Preferably, W0 ≤ (2 + 2 a) Z4.

If the relationship of W0 ≤ (3 + 2a) Z4 is not satisfied, the formed film becomes sticky, and bleeding of additives and low molecular weight components tends to occur, which is not preferable. W0 is determined from the elution curve obtained by the measurement method of the temperature-raising fractionation chromatograph described in the “Evaluation Method for Resin Properties” in Example.

In addition, as the propylene-ethylene copolymer [A] in the present invention, in addition to the above requirements, the melting point (Tm 0C) of the copolymer measured by a differential scanning calorimeter (DSC) and a are represented by the following formulas. Preferably, the relationship of (1) is satisfied.

Tm≤ 1 60— 5 a · · · (1)

More preferably, Tm≤ 160— 6 a · · · (2)

Is satisfied.

If this relationship is not satisfied, the heat sealing property tends to be insufficient, and the anti-blocking property may decrease. As a method for measuring the melting point (Tm (¾)) of the copolymer using a differential scanning calorimeter (DSC), there is a method using a DSC 7 type differential scanning calorimeter manufactured by PerkinElmer Inc. . That is, 1 Omg of the sample is melted in advance in a nitrogen atmosphere at 230 min for 3 min, and then the temperature is lowered to 201 at 10 t / min. After keeping the temperature at this temperature for 3 min, the temperature is raised at 1 O ^ Zmin, and the melting point is determined by the peak top temperature of the maximum peak of the melting endothermic curve.

Furthermore, as the propylene-ethylene copolymer [A] in the present invention, the component on the high-temperature side of the main elution peak of the temperature-raising fractionation chromatograph contributes to moldability and rigidity such as chill roll release. It is preferable that a certain amount is present rather than absent. In the present invention, the amount (WH (% by weight)) eluted in the temperature range of (Tp + 5) t or more in [A] and a More preferably satisfies the following relationship.

0.1 ≤ WH ≤ 3 a

Particularly preferably,

WH ≤ (3 a-3), and (3 a— 1 5) ≤WH

Meet. WH is determined from the elution curve obtained by the measurement method of the temperature-increased fractionation chromatograph described in the “Method for evaluating resin characteristics” in the same manner as described above.

Further, as the propylene-ethylene copolymer [A] in the present invention, the amount of the extractable component (E (% by weight)) of the boiling garbage ether is 2.5% by weight or less, and E and a have the following relationship. Is preferably satisfied.

E≤ (2 a + 1 5) / 1 0 More preferably,

Ε≤ (α + 5) / 5

Meet. Satisfying the above relationship is preferable because the formed film does not become sticky. For Ε, add 3 g of pellets crushed to the size of lmm0 mesh path in a cylindrical filter paper and add 16 Oml of extraction solvent getyl ether to a flat-bottomed flask. Perform Soxhlet extraction for 0 hours, and after the extraction is completed, recover getyl ether using a rotary evaporator and dry it to a constant weight with a vacuum dryer to obtain.

Further, the propylene-ethylene copolymer [A] in the present invention preferably has a menoleto index (MI Omin) of 0.1 to 200 g / 1 Omin, and I to 40 g / I0 min. Is more preferable, and 2 to 20 g / l Omin is particularly preferable. If the melt index is out of this range, the moldability may be poor. MI (g / 10min) is measured according to JIS K7210 at a temperature of 230 and a load of 2160 g.

Further, as the propylene-ethylene copolymer [A] in the present invention, the stereoregularity index (P (mol%) in the copolymer measured by ¹³ C-NMR described in Example “Method for evaluating resin properties” was used. ) Is preferably 98 mol% or more, more preferably 98.5 mol% or more. If the stereoregularity index P is less than 98 mol%, the rigidity and antiblocking properties of the formed film may be insufficient.

The propylene-ethylene copolymer [A] in the present invention is not particularly limited as long as it is obtained by copolymerizing propylene and ethylene, but a propylene-ethylene random copolymer is preferred.

[2] Propylene-ethylene copolymer [B] The propylene-ethylene copolymer [B] in the present invention needs to have an ethylene content of 10 to 25% by weight. Preferably, it is 15 to 25% by weight. If the ethylene content of [B] is less than 10% by weight, the impact resistance is undesirably reduced. On the other hand, if it exceeds 25% by weight, transparency is reduced. In addition to the above-mentioned requirements, the copolymer [B] preferably has an intrinsic viscosity [135] measured in a tetralin solvent of 0.1 to 5 dL.

Further, in the present invention, the component amount () (% by weight) and the tensile modulus (TM) (MPa) of the component [B] in the propylene-based copolymer have the following relationship.

When TM <2 × 10 ⁵ X (β) “ ^L? ” ^Is satisfied, the balance between flexibility and transparency of the film obtained by film formation is excellent. For example, the tensile modulus is 100 OMPa or less, and the haze is 1 A film of less than 5% is obtained.

Particularly preferably, the following relationship

TM 10 ⁵ X (β) — ^{1 6}

Meet. For example, a film having a tensile modulus of 100 OMPa or less and a haze of 10% or less can be obtained.

The propylene-ethylene copolymer [B] in the present invention is not particularly limited as long as it is obtained by copolymerizing propylene and ethylene, but a propylene-ethylene random copolymer is preferred.

[3] Method for Producing Propylene-Ethylene Copolymers [A] and [B] The method for obtaining the propylene-ethylene copolymers [A] and [B] includes, for example, (A) magnesium compound, titanium compound A solid catalyst component obtained by contacting an electron-donating compound and, if necessary, a silicon compound. And a production method in which ethylene and propylene are copolymerized in the presence of (B) an organoaluminum compound and, if necessary, (C) a catalyst comprising an electron-donating compound as the third component.

Preferably, (A) a solid catalyst component obtained by contacting and reacting a magnesium compound, a titanium compound, and an electron donating compound, (B) an organic aluminum compound, and (C) a compound represented by the following general formula (I)

S i R ¹² (OR ² ) 2 (I) (wherein, R ¹ represents a branched hydrocarbon group having 1 to 20 carbon atoms or a saturated cyclic hydrocarbon group, and R ² represents A straight-chain hydrocarbon group or a branched-chain hydrocarbon group having a number of 1 to 4, which may be the same or different from each other. In the presence of, a production method in which ethylene and propylene are copolymerized.

More preferably, (A) after contacting at a temperature of from 120 to 150 in the presence of a magnesium compound, a titanium compound, an electron donating compound and, if necessary, a silicon compound, at a temperature of from 100 to 150 ° In the presence of a solid catalyst component obtained by washing with an inert solvent in (A), (B) an organic aluminum compound, and, if necessary, (C) a catalyst comprising an electron donating compound as the third component, ethylene and A production method of copolymerizing propylene is exemplified.

Particularly preferably, (A) a dialkoxymagnesium, an ester compound, and the following general formula (II)

S i (OR ³ ) _m X ^L ₄ — _m · · · (II)

(In the formula, R ³ represents an alkyl group, a cycloalkyl group, or an aryl group, X ¹ represents a halogen atom such as chlorine or bromine, and m represents a real number between 0 and 3.0. Show. ) By reacting a reaction product obtained by reacting the silicon compound represented by with a titanium tetrahalide at a temperature of 12 to 15;

A solid catalyst component obtained by washing with a hydrocarbon solvent at a temperature of 80 to 15; (B) an organoaluminum compound; and a catalyst comprising the organosilicon compound represented by the general formula (I). And a production method in which ethylene and propylene are copolymerized.

Hereinafter, each of the above catalyst components and a method for preparing the same, a method for copolymerizing ethylene and propylene, and the like will be described.

(A) Solid catalyst component

The solid catalyst component contains magnesium, titanium and an electron donor, and comprises the following (a) a magnesium compound, (b) a titanium compound,

(c) It is formed from a solid catalyst component comprising an electron donating compound and, if necessary, a silicon compound (d).

(a) Magnesium compound

The magnesium compound is not particularly limited, but a magnesium compound represented by the general formula (III) Mg R ⁴ R ⁵ ··· (III) can be preferably used. In the above general formula (III), R ⁴ and R ⁵ represent a hydrocarbon group, an OR ⁶ group (R ⁶ is a hydrocarbon group) or a halogen atom. Examples of the hydrocarbon group R ⁴ Contact and R ^5, the number 1 to 1 2 alkyl group carbon atoms, a cycloalkyl group, Ariru group, a Ararukiru group. Examples of OR ⁶ group, R ⁶ carbon atoms 1 to 12 alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, etc .; halogen atoms include chlorine, bromine, iodine, fluorine, etc.

] 2 Can be mentioned. R ⁴ and R ⁵ may be the same or different.

Specific examples of the magnesium compound represented by the above general formula (III) include dimethylmagnesium, getylmagnesium, diisopropylmagnesium, dibuty / lemagnesium, dihexinolemagnesium, dioctinolemagnesium, ethinolebutino. Azolequinolemagnesium, such as remagnesium, diphene / remagnesium, dicyclohexenolemagnesium, and other magnesium salts; dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dihexyloxymagnesium Magnesium, dioctoxymagnesium, diphenoxymagnesium, dihexoxymagnesium hexyloxymagnesium, etc., aryloxymagnesium; ethylmagnesium chloride, butyl Magnesium chloride, hexinole magnesium chloride, isopropyl magnesium chloride, isobutyl magnesium chloride, t-butylmagnesium chloride, feninole magnesium bromide, benzil / le magnesium chloride, ethyl magnesium Bromide, butylmagnesium bromide, phenylmagnesium chloride, butylmagnesium iodide, etc., magnesium halides, arylene magnesium halides; butoxymagnesium chloride, cyclohexyloxymagnesium chloride Magnesium, chloride, ethoxymagnesium chloride, ethoxymagnesium bromide, butoxymagnesium bromide, ethoxymagnesium iodide, etc. Shiumuharaido; salts of magnesium, magnesium bromide, and the like can be given magnesium halide such as magnesium iodide.

Among these magnesium compounds, from the viewpoint of polymerization activity and stereoregularity, magnesium halides, magnesium alkoxides, and alkyl sesame Gnesium and alkylmagnesium halides can be suitably used.

The above magnesium compound can be prepared from a compound containing metallic magnesium or magnesium.

—Examples include contacting metal magnesium with halogens and alcohols.

Here, examples of the halogen include iodine, chlorine, bromine, and fluorine. Of these, iodine is preferred. Examples of alcohols include methanol, ethanol, propanol, butanol, cyclohexanol, octanol and the like. Further, as another example, a magnesium dialkoxy compound represented by Mg (OR ⁷ ) 2 (where R ⁷ represents a hydrocarbon group having 1 to 20 carbon atoms).

)) Is contacted with a halide. Further, the magnesium dialkoxy compound may be brought into contact with a halide in advance. Examples of the halide include gay tetrachloride, silicon tetrabromide, tin tetrachloride, tin tetrabromide, hydrogen chloride and the like. Of these, silicon tetrachloride is preferred from the viewpoint of polymerization activity and stereoregularity. R ⁷ is an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group and an octyl group; a cyclohexyl group, an aryl group and a propenyl group. And alkenyl groups such as butyr group; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as phenethyl and 3-phenylpropyl group. Among them, an alkyl group having 1 to 10 carbon atoms is particularly preferable.

Further, the magnesium compound may be supported on a support such as silica, alumina, and polystyrene. The above magnesium compounds may be used alone or in combination of two or more. Also, It may contain halogen such as nitrogen, other elements such as silicon and aluminum, and may contain electron donors such as alcohols, ethers and esters.

(b) Titanium compound

The titanium compound is not particularly limited, but has the general formula (IV)

T i X ¹ _p (OR ⁸ ) 4-p * * * (IV)

Can be preferably used.

In the above general formula (IV), X ¹ represents a halogen atom, and among them, a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. R ⁸ is a hydrocarbon group, which may be a saturated group or an unsaturated group, may be a linear group, a group having a branched chain, or a cyclic group. It may contain a hetero atom such as oxygen, oxygen, silicon and phosphorus. Preferably, it is a hydrocarbon group having 1 to 10 carbon atoms, particularly an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and an aralkyl group, and a linear or branched alkyl group is particularly preferred. When a plurality of OR ⁸ are present, they may be the same or different from each other. Specific examples of R ⁸ include methyl, ethyl, n-propyl, isopropyl, n-butynole, sec-butynole, isobutynole, n-pentynole, n-hexynole, and n-heptyl. Group, n-octynole group, n-decinole group, aryl group, butyr group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group, phenethyl group, etc. . p shows the integer of 0-4.

Specific examples of the titanium compound represented by the above general formula (IV) include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, Tetraalkoxytitanium such as tetraisobutoxytitanium, tetracyclohexyloxytitanium, and tetraphenoxytitanium; titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; methoxytitanium trichloride, ethoxytitanium trichloride; Alkoxy titanium trihalides such as propoxytitanium trichloride, n-butoxytitanium trichloride and ethoxytitanium tribromide; dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, The

— Dihalogenated dialkoxytitanium such as n-propoxytitanium dichloride and ethoxytitanium dibromide; trimethoxytitanium chloride, triethoxytitanium chloride, triisopropoxytitanium chloride, tri-n-propoxytitanium chloride, Monohalogenated trialkoxy titanium such as tree n-butoxy titanium chloride and the like can be mentioned. Among them, a titanium compound having a high halogen content, particularly titanium tetrachloride, is preferable from the viewpoint of polymerization activity. These titanium compounds may be used alone or in combination of two or more.

(c) electron donating compound

Examples of the electron donating compound include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, esters of organic acids and inorganic acids, and ethers such as monoether, diether and polyether; Examples thereof include nitrogen-containing electron donating compounds such as ammonia, amine, nitrile, and isocyanate. Examples of the organic acid include a carboxylic acid, for example, malonic acid.

Among these, esters of polycarboxylic acids are preferred, and esters of aromatic polycarboxylic acids are more preferred. From the viewpoint of polymerization activity, monoesters and / or diesters of aromatic dicarboxylic acids are particularly preferred. In addition, the organic group in the ester moiety is a linear, branched or cyclic fatty Group hydrocarbons are preferred.

Specifically, phthalic acid, naphthalene-l, 2-dicarboxylic acid, naphthalene-l, 3-dicanolevonic acid, 5,6,7,8-tetrahydronaphthalene-l, 2-dicarboxylic acid, 5,6 , 7,8-Tetrahydronaphthalene-2,3-dicanolevonic acid, indane-1,4,5-dicarboxylic acid, indane-5,6-dicarboxylic acid and other dicarboxylic acids such as methyl, ethyl, n-propynole, isopropynole, n-Petit / re, isobutynole, t-buty / re, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylbutyl pill, 1-methynolepentinole, 2-methylpentyl , 3-methinolepentinole, 4-methinolepentinole, 1-echinolebutinole, 2-echinolebutinole, n-hexinole, cyclohexinole, n-heptinolle, n-octyl, n- Nonyl, 2-methylhexynole, 3-methylhexyl, 4-methylethynolexylene, 2-ethynolehexynole, 3-ethynolehexynole, 4-ethynolehexynole, 2-methynolepentinole, 3-methynolepentyl, Examples thereof include dialkyl esters such as 2-ethylenpentyl and 3-ethylpentyl. Of these, phthalic acid diesters are preferred, and linear or branched aliphatic hydrocarbons having 4 or more carbon atoms in the organic group in the ester portion are preferred.

Specific examples thereof include di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, and getyl phthalate.

These compounds may be used alone or in combination of two or more.

(d) Silicon compound

In the preparation of the solid catalyst component, in addition to the components (a), (b) and (c), a component (d) may be optionally used as a component (d) below,

(In the formula, R ³ represents an alkyl group, a cycloalkyl group, or an aryl group, X ¹ represents a halogen atom such as chlorine or bromine, and m represents a real number between 0 and 3.0.) Can be used. By using a silicon compound, the catalytic activity and stereoregularity can be improved, and the amount of fine powder in the produced polymer can be reduced. In the above formula (II), R ³ represents an alkyl group, a cycloalkyl group or an aryl group. As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutynole, n-pentynole, n-hexynole, and n-heptynole. Group, n-octyl group, n-decyl group and the like. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cyclohexenyl group. Examples of the aryl group include a phenyl group, a tolyl group, a benzyl group, and a phenyl group. X ¹ represents a halogen atom such as chlorine or bromine, and among these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. m indicates a real number between 0 and 3.0.

Specific examples of the silicon compound represented by the above general formula (II) include silicon tetrachloride, methoxytrichlorosilane, dimethoxydichlorosilane, trimethoxycyclosilane, ethoxytrichlorosilane, ethoxydichlorosilane, triethoxychlorosilane, and the like. Propoxytrichlorosilane, dipropoxydichlorosilane, tripropoxychlorosilane and the like can be mentioned. Of these, silicon tetrachloride is particularly preferred. Each of these silicon compounds may be used alone, or two or more of them may be used in combination.

(B) Organoaluminum compound The organic aluminum compound (B) used in the production of the crystalline polypropylene of the present invention is not particularly limited, but preferably has an alkyl group, a halogen atom, a hydrogen atom, an alkoxy group, an aluminoxane and a mixture thereof. be able to. Specifically, trimethylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, etc .; getylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride And monochloride; methyl chloride; methyl chloride; methyl chloride; methyl chloride; methyl chloride; methyl ethyl chloride; methyl chloride; methyl chloride; methyl chloride; methyl chloride; methyl chloride; methyl chloride Chain aluminoxane such as aluminoxane and the like can be mentioned. Among these organoaluminum compounds, trialkylaluminums having a lower alkyl group having 1 to 5 carbon atoms, particularly trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferred. Further, these organic aluminum compounds may be used alone or in combination of two or more.

(C) Third component (Electron donating compound)

To produce the propylene random copolymer of the present invention, (C) an electron donating compound is used. As the (C) electron donating compound, an organic silicon compound having a Si—O—C bond, a nitrogen-containing compound, a phosphorus-containing compound, and an oxygen-containing compound can be used. Among these, from the viewpoints of polymerization activity and stereoregularity, it is preferable to use organic silicon compounds having a Si—O—C bond, ethers and esters, and particularly to have an Si—O—C bond. It is preferable to use an organic silicon compound.

Specific examples of the organic silicon compound having the Si—O—C bond include: Tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, ethynoleisopropinoresime methoxysilane, propinoleisopropyl ^ dimethoxymethoxysilane, diisopropyldimethoxymethoxysilane Toxoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, g-tert-butyldimethoxysilane, t-butynolemethinoresimethoxysilane, t-butinoethyldimethoxysilane, t-butylpropyldimethoxysilane, t-butylisopropyldimethoxysilane, t-butyl Butinoresime methoxy silane, t-butyl isobutyl dimethoxy silane, t-butyl (S Butyl) dimethoxysilane, t-butynoleaminoresimethoxysilane, t-butynolehexyldimethoxysilane, t-butylheptyldimethoxysilane, t-butinoleocty ^^ dimethoxysilane, t-butynolenoninoresimeethoxysilane, t-butyldecyldimethoxysilane, t-Butyl (3,3,3-trifluoromethylpropyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexinoleetinoresime ethoxysilane, cyclohexylolepropinoresime ethoxysilane, cyclopentinole-t-butinoresime methoxy silane , Cyclohexinole-butinoresin methoxy silane, dicyclopentinolesin methoxy silane, dicyclohexinoresin ethoxy silane, bis (2-methylcyclopentyl) dimethyl Silane, bis (2,3-dimethylcyclopentynole) dimethoxysilane, dipheninoresimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, provisotrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltrimethoxysilane , S-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentene Noretrimethoxysilane, cyclohexenoletrimethoxysilane, norebonolenanantrimethoxysilane, indenyltrimethoxysilane, 2-methylcyclopentinoletrimethoxysilane, cyclopentynole (t-butoxy) dimethoxysilane, isopropyl (t-butoxy) dimethoxyisobutyl, t-butyl Dimethoxysilane, t-butyl (t-butoxy) dimethoxysilane, texyltrimethoxysilane, texylisopropoxydimethoxysilane, texinole (t-butoxy) dimethylethoxysilane, texinolemethine resin methoxysilane, texinoleethino resin methoxysilane, texinoleisopropine Noresimetoxysilane, texinolecyclopentyldimethoxysilane, texil myristi Dimethyl Tokishishiran, Kishirujime Tokishishiran like to thexyl cycloalkyl.

In addition, as an organic silicon compound, the following general formula (V)

R ^! OR ¹ R

_{CH ~ ec H 2 • S i} ~ c H 2 → - -C- -RI 2 (V)

O R 1 5 R 1 3

(Wherein, R ⁹ to R ^U represents a hydrogen atom or a hydrocarbon group, they may be the same or different, may form a ring together with the adjacent group. R ¹² and R ^{And 13} represents a hydrocarbon group, which may be the same or different, and may be bonded to an adjacent group to form a ring R ¹⁴ and R ^{15 each} have 1 to 20 carbon atoms And m is an integer of 2 or more, and n is an integer of 2 or more.), And an organic silicon compound represented by the following formula: Specifically, R ⁹ ~ R ¹¹ is a linear hydrocarbon group such as a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group; a branched hydrocarbon group such as an isopropyl group, an isobutyl group, a t-butyl group or a texyl group; And saturated cyclic hydrocarbon groups such as a cyclopentyl group and a cyclohexyl group, and unsaturated cyclic hydrocarbon groups such as a phenyl group and a pentamethylphenyl group. Of these, preferred are hydrogen and a linear hydrocarbon group having 1 to 6 carbon atoms, and particularly preferred are hydrogen, methyl and ethyl.

R ¹² and R ¹³ are linear hydrocarbon groups such as methyl group, ethyl group and n-propyl group; branched hydrocarbon groups such as isopropyl group, isobutyl group, t-butyl group and texyl group; And saturated cyclic hydrocarbon groups such as a cyclopentyl group and a cyclohexyl group, and unsaturated cyclic hydrocarbon groups such as a phenyl group and a pentamethylphenyl group. Also, these may be the same or different. Among these, a linear hydrocarbon group having 1 to 6 carbon atoms is preferable, and a methyl group and an ethyl group are particularly preferable.

As R ¹⁴ and R ¹⁵ , methyl, ethyl, n-propyl, isopropynole, n-butynole, isobutyl, sec-butynole, t-butyl, n-pentyl, n— Examples thereof include a linear or branched alkyl group such as a xyl group and an n-octynole group. They may be the same or different. Among these, a linear hydrocarbon group having 1 to 6 carbon atoms is preferable, and a methyl group is particularly preferable.

Specific preferred examples of the silicon compound represented by the above general formula (V) include neopentyl n-propyldimethoxysilane, neopentyl n-butyldimethoxysilane, neopentyl n-pentyldimethoxysilane, neopentinole n-hexinoresime ethoxysilane, and neopentynolene. n —Heptyl dimethoxy silane, isobutyl n-propyl dimethoxy silane, isobutynole n-buty ^^ dimethoxy silane, isopti / le n-pentynole dimethoxy silane, isobutyl n—hexyl dimethoxy silane, isobutyl n-heptyl dimethoxy silane, 2-cyclohexyl Propyl n-propyl pinoresinethoxysilane, 2-cyclohexinolebutynole n-propyldimethoxysilane, 2-cyclohexinolepentynole n-propinoresinethoxysilane, 2-cyclohexinolehexyl / n-propinoresinethoxysilane, 2- Cyclohexinole heptinole n-propinoresimethoxysilane, 2-cyclopentinolepropynole n-propinoresimethoxysilane, 2-cyclopentylbutyl n-propyldimethoxysilane, 2-cyclopente Rupentyl n-propinoresime ethoxysilane, 2-cyclopentinolehexynole n-propinoresime methoxysilane, 2-cyclopentylheptyl heptyl n-propyldimethoxysilane, isopentynole n-propimedimethoxysilane, isopentyl η-butyldimethoxysilane, isopentyldimethyl Sisilane, isopentyl _η- hexyldimethoxysilane, isopentyl _η- heptinoresimethoxysilane, isopentinoleisobuty ^^ dimethoxysilane, isopentylneopenti / resimethoxysilane, diisopentinoresimethoxysilane, diisoheptidimethoxysilane, diisohe Xy / resistoxy silane and the like. Specific examples of particularly preferred compounds include neopentyl η-propyl dimethoxy silane, neopentyl η-pentino res ethoxy silane, isopentino leneo pentino resie methoxy silane, diisopenti dimethyl silane, diisoheptino resie methoxy silane, and diisohexyl dimethoxy silane. Specific examples of more preferred compounds include neo- pliers / re-η- pliers / resimethoxysilane and diisobentyldimethoxysilane.

The silicon compound represented by the above general formula (V) can be prepared by any method. Can be synthesized. A typical synthetic route is as follows.

[1] [2]

[2]

Or

(2) ^{1 2}

In this synthetic route, the raw material compound [1] is commercially available or can be obtained by known alkylation, halogenation and the like. The compound [1] is represented by the general formula (V) by a known Grignard reaction. Organic silicon compounds can be obtained.

These organic silicon compounds may be used alone or in combination of two or more.

Specific examples of the nitrogen-containing compound include 2,6-diisopropylpiberidine, 2,6-diisopropinole 4-methinolepiperidine, and N-methinole 2,2,6,6-tetramethylpiperidine. 6, 5-substituted azolidines such as 2,5-diisopropylazolidine, N-methyl 2,2,5,5-tetramethylazolidine; N, N, N, , N, 1-tetramethylmethylenediamine, substituted methylenediamines such as N, N, N,, N, -tetraethylmethylenediamine; 1,3-dibenzinoreimidazolidine, 1,3-dipentinoley 2-phenyl Substituted imidazolidines such as ninoleimidazolidin and the like can be mentioned.

Specific examples of the phosphorus-containing compound include triethyl phosphite, tri-n-propynolephosphite, triisopropynolephosphite, tri-n-butyl phosphite, triisobutyl phosphite, getyl n-butyl phosphite, Esthenol phosphites such as getinolefeninolephosphite and the like.

Specific examples of the oxygen-containing compound include 2,2,6-substituted tetrahydrofurans such as 2,2,6,6-tetramethyltetrahydrofuran, 2,2,6,6-tetraethynoletetrahydrofuran, and 1,1-dimethoxy. Examples include 1,2,3,4,5-tetrachlorocyclopentadiene, 9,9-dimethoxyfluorene, dimethoxymethane derivatives such as diphenyldimethoxymethane.

The method for preparing the solid catalyst component (A) includes the following (a) a magnesium compound, (b) a titanium compound, (c) an electron donor, and Accordingly, (d) the silicon compound may be brought into contact by a usual method except for the temperature, and the contact procedure is not particularly limited. For example, each component may be brought into contact in the presence of an inert solvent such as a hydrocarbon, or each component may be contacted after being diluted with an inert solvent such as a hydrocarbon. Examples of the inert solvent include, for example, aliphatic hydrocarbons such as octane, decane, and ethylcyclohexane, alicyclic hydrocarbons, and mixtures thereof.

Here, the titanium compound is magnesium of the above magnesium compound

Usually, 0.5 to: L00 mol, preferably 1 to 50 mol is used per 1 monol. If the molar ratio is outside the above range, the catalytic activity may be insufficient. The electron donor is used in an amount of usually 0.01 to 10 mol, preferably 0.05 to 1.0 mol, per 1 mol of magnesium of the above magnesium compound. If the molar ratio is outside the above range, catalytic activity and stereoregularity may be insufficient. Furthermore, when a silicon compound is used, it is usually 0.001 to: L00 monolith, preferably 0.005 to 1 mol of the magnesium compound of the above-mentioned magnesium compound.

Use 5.0 moles. If the molar ratio is outside the above range, the effect of improving the catalytic activity and stereoregularity may not be sufficiently exhibited, and the amount of fine powder in the produced polymer may increase.

The above components (a) to (d) are brought into contact with each other after all components have been added.

5 O ^t t, preferably carried out at a temperature in the range of 1 25 to 14. If the contact temperature is outside the above range, the effect of improving the catalytic activity and stereoregularity will not be sufficiently exhibited. Also, the contact is usually 1 minute to 24 hours, preferably 10 minutes to

Done for 6 hours. When using a solvent, the pressure range varies depending on the type of solvent, the contact temperature, etc., but it is usually in the range of 0 to 50 kg / cm ² G, preferably in the range of 0 to 10 kg / cm ² G. Perform at In addition, during the contact operation, it is preferable to perform agitation in terms of contact uniformity and contact efficiency. New

Further, it is preferable that the titanium compound is contacted twice or more to sufficiently support the magnesium compound serving as a catalyst carrier.

When a solvent is used in the contacting operation, the solvent is usually used in an amount of 5,000 milliliters or less, preferably 10 to 100 milliliters per mole of the titanium compound. If this ratio deviates from the above range, contact uniformity and contact efficiency may be deteriorated.

The solid catalyst component obtained by the above contact is washed with an inert solvent at a temperature of 100 to 150, preferably 120 to 140. If the washing temperature is outside the above range, the effect of improving the catalytic activity and stereoregularity will not be sufficiently exhibited. Examples of the inert solvent include aliphatic hydrocarbons such as octane and decane; alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane; aromatic hydrocarbons such as toluene and xylene; tetrachloroethane; Examples thereof include halogenated hydrocarbons such as carbons and mixtures thereof. Of these, aliphatic hydrocarbons are preferably used.

The washing method is not particularly limited, but a method such as decantation and filtration is preferable. There is no particular limitation on the amount of the inert solvent used, the washing time, and the number of washings, but usually 100 to L: 100,000 milliliters, preferably 1,000 to 50,000 milliliters of solvent per mole of magnesium compound. The reaction is usually performed for 1 minute to 24 hours, preferably for 10 minutes to 6 hours. If this ratio deviates from the above range, cleaning may be incomplete.

In this case, the pressure, type of solvent, such as by washing temperature, but its range is change, usually, 0~50 k gZc m ² G, preferably, 0 to: 1 0 k Perform in the range of cm ² G. Further, during the washing operation, it is preferable to perform stirring from the viewpoint of uniformity of washing and washing efficiency.

The obtained solid catalyst component can be stored in a dry state or in an inert solvent such as a hydrocarbon.

Copolymerization method>

The method of copolymerizing ethylene and propylene in the present invention may be any method such as a gas phase polymerization method, a solution polymerization method, a slurry polymerization method, a bulk polymerization method, etc., but the copolymer [A] or As the polymerization method for producing [B], a gas phase polymerization method in which the copolymerization component is incorporated into the polypropylene-based copolymer without elution and the yield to consumed olefins is high and industrially advantageous is preferable. The amount of the catalyst component used is not particularly limited, but the solid catalyst component (A) is usually used in an amount of 0.0005 to 1 mmol per liter of reaction volume in terms of titanium atoms. And

As the organoaluminum compound as the component (B), the atomic ratio of aluminum and titanium is usually 1 to 1000, preferably 10 to 500. If the atomic ratio is outside the above range, the catalytic activity may be insufficient. Also,

(C) When an electron donating compound such as an organic silicon compound is used as the third component, the molar ratio of (C) the electron donating compound Z (B) the organoaluminum compound is usually 0.001 to 5.0, preferably Is used from 0.01 to 2.0, more preferably from 0.05 to 1.0. If the molar ratio is outside the above range, sufficient catalytic activity and stereoregularity may not be obtained. However, when the prepolymerization described below is performed, the amount can be further reduced. Further, in the present invention, from the viewpoints of polymerization activity, stereoregularity and polymer padder form, if desired, first, prepolymerization of olefin may be carried out, followed by main polymerization. In this case, the (A) solid catalyst component, (B

) Organoaluminum compound and, if necessary, (C) electron donating compound Are pre-polymerized in the presence of a catalyst, each of which is mixed at a predetermined ratio, at a temperature in the range of usually 1 to 1 ° O at normal pressure or a pressure of about 50 kg / cm ² G. In the presence of and a prepolymerized product, propylene and ethylene as a comonomer are fully polymerized. The olefin used for the prepolymerization is represented by the following general formula (VI)

R ^ID -CH = CH ₂ (VI)

Α-olefin is preferred.

In the above general formula (VI), R ¹⁶ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group may be a saturated group or an unsaturated group. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methylino 1-pentene, 4-methylene 1-pentene, Biercyclohexane, butadiene, isoprene, piperylene and the like can be mentioned. These olefins may be used alone or in combination of two or more. Among the above-mentioned olefins, ethylene and propylene are particularly preferable.

In the present invention, the polymerization conditions are different depending on the polymerization method. For example, in the case of a gas phase polymerization method, the polymerization temperature is preferably 50 to 100ί, more preferably 60 to 90, using the above-mentioned catalyst. In the range. If the polymerization temperature at this time is 50 or less, the transparency of the produced propylene-based copolymer may decrease. The polymerization pressure is in the range of 1 to 100 _{kg /} cm ² G, preferably 1 to 50 kg cm ² G, and the polymerization is carried out while introducing a mixed gas of propylene and ethylene. The polymerization time depends on the polymerization temperature of the raw materials propylene and ethylene and cannot be determined unconditionally, but is usually 5 minutes to 20 hours, preferably about 10 minutes to 10 hours. The mixing ratio of propylene and ethylene depends on the polymerization temperature and pressure, etc. Although it is not possible, it is preferable to adjust the mixing ratio so that the ethylene content of the copolymer [A] is different from that of the copolymer [B]. Usually, when producing the copolymer [A], the volume ratio of propylene Z ethylene (vol Zv o 1) is (50/1) to (5/1), preferably (30Z1) to (7/1 ). In the case of producing the copolymer [B], the volume ratio of propylene / ethylene (vol / vol) (8/1) to (3Z2), preferably (4/1) to (21) is there.

The molecular weight of the copolymer can be adjusted by adding a chain transfer agent, preferably by adding hydrogen. Further, an inert gas such as nitrogen may be present.

In the present invention, the component (A), the component (B) and the component (C) of the catalyst component are mixed at a predetermined ratio and brought into contact, and then propylene and ethylene are immediately introduced to carry out polymerization. May be performed, or after contact, 0.2

After aging for about 3 hours, propylene and ethylene may be introduced to carry out polymerization. Further, the catalyst component can be supplied by suspending in an inert solvent or propylene.

[4] Method for producing propylene-based copolymer

Next, a method for producing the propylene-based copolymer of the present invention will be described. Examples of the method for producing the propylene copolymer of the present invention include a method of blending the above-mentioned propylene-ethylene copolymers [A] and [B]. The method of blending may be powder blending using a Banbury mixer or a twin-screw kneader, or a reactor blending in which the copolymer is polymerized and blended in a polymerization tank. Reactor blends are preferred because they are good and the resulting propylene-based copolymer has excellent flexibility and the like.

As a reactor blend, propylene and ethylene are co- And a method of producing by a propylene block copolymerization method. Specifically, a production method in which the propylene-ethylene copolymers [A] and [B] are subjected to multi-stage polymerization using propylene and ethylene is exemplified. For example, there is a production method in which the ethylene-propylene copolymer [A] is polymerized in the first stage, and the ethylene-propylene copolymer [B] is polymerized in the second stage. [A] and [B] may be polymerized in either the first-stage polymerization or the second-stage polymerization, but it is preferable that [A] be polymerized in the first stage and [B] be polymerized in the second stage. Further, as the polymerization method in the multi-stage polymerization, either batch polymerization or continuous polymerization can be applied.

The polymerization conditions of the first and second stages in the multi-stage polymerization include the above-mentioned polymerization conditions. If necessary, a molecular weight modifier such as hydrogen may be added. The ratio between the copolymers [A] and [B] may be adjusted by the polymerization time and the polymerization pressure.

In the propylene copolymer of the present invention, the post-treatment after the polymerization can be carried out by a conventional method. That is, in the gas phase polymerization method, after the polymerization, the polymer powder derived from the polymerizer may be passed through a nitrogen gas stream or the like in order to remove olefins and the like contained therein. Depending on the conditions, pelletization may be performed by an extruder. At that time, a small amount of water, alcohol, or the like may be added to completely deactivate the catalyst. In the bulk polymerization method, after polymerization, the monomer can be completely separated from the polymer discharged from the polymerization vessel and then pelletized.

The propylene-based copolymer of the present invention can be used in combination with another polypropylene-based resin. Other polypropylene resins include polypropylene homopolymer, ct-olefin content other than propylene (α-olefins include, for example, at least one kind of ethylene, 1-butene, 1-pentene, 1-hexene, etc.) Of 15% by weight or less _α -olefin homopolymer, propylene block copolymer, random block copolymer and the like. In addition, at the time of blending, known antioxidants, neutralizing agents, antistatic agents, weathering agents, antiblocking agents, and the like used in conventional polyolefins can be added as necessary.

[I I] Molded body

The molded article of the present invention is a molded article obtained by molding the propylene-based copolymer by various molding methods such as injection molding, extrusion molding, and thermoforming. As molded articles, films, sheets, and urns are particularly preferred since they have flexibility and good transparency. Further, the molded article may be subjected to a stretching treatment or the like as secondary processing. For example, as the molded product subjected to the stretching treatment, a uniaxially stretched film, a biaxially stretched film, a fiber and the like can be mentioned. The film in the present invention is a film obtained by forming the above-mentioned propylene-based copolymer into a film, and has an advantage of being excellent in transparency. The film of the present invention usually has a haze of 15% or less. Preferably, the haze is at most 10%. The method for producing the film is not particularly limited, and includes a usual T-die casting method. That is, various additives can be formulated into the propylene-based copolymer powder as required, extruded and granulated by a kneader, pelletized, and formed into a T-die cast film. Usually, the propylene-based copolymer of the present invention has a thickness of 10 to 500 μm by a T-die casting film forming method even under a high film forming condition of a take-up speed of 50 m / "min or more. In addition, because of the above-mentioned favorable properties, it can be suitably used as at least one layer component in the production of a laminated film by a co-extrusion film-forming method. It can also be used as a multi-layer by extrusion lamination with resin or co-extrusion molding, etc. In the film forming method, high-speed film forming is performed by large-scale manufacturing. The T-die casting film forming method is preferred, but not limited thereto, and any film forming method may be used as long as a film can be manufactured by a melt extrusion molding method.

The following examples can be given as specific examples of the additive formulation.

Example of additive formulation (A)

① Antioxidant

Cilba Specialty Chemicals, Inc.

： 1000 ρ ρ m Cinvas ぺ Inoregafoss 168

: 1000 p pm

② Neutralizer

Stearic acid power / Resistance: 1000 ppm

③ Anti-blocking agent

Fuji Silica's silica-based anti-blocking agent: 1000 ppm

④Slip agent

Erucamide: 250 ppm

Example of additive formulation (B)

① Antioxidant

Cilba Specialty Chemicals Inc. Irganox 1 010

： 1000 ρ ρ m Chivas ぺ Shanoreti Chemi Power / Inoregafoss 168

: 1000 p pm

② Neutralizer

Calcium stearate: 1000 ppm

③ Anti blocking agent

Fuji Silica's silica anti-blocking agent: 2300 ppm ④Slip agent

Erucamide: 500 ppm Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

First, the measuring method in the present invention will be described. The measuring methods used in Examples and Comparative Examples of the present invention are the following “resin property evaluation method” and “film quality evaluation method”.

`` Resin property evaluation method ''

① Measurement of α and P by ¹³ C-NMR

^The spectrum of ¹³ C-NMR was measured under the following conditions using a JNM-EX400 type NMR apparatus manufactured by JEOL Ltd.

Sample concentration: 22 Omg NMR solvent 3m 1

NMR solvent (volume ratio):

1, 2, 4—Trichloro benzene Z benzene one d 6 = 9 OZ 10 Measurement temperature: 1 30Χ:

Pulse width: 45 °

Pulse repetition time: 4 seconds

Number of accumulation: 4000 times

Table 1 shows the assignment of each signal of the obtained propylene-based random copolymer. Ρ indicates a propylene unit and Ε indicates an ethylene unit. Therefore, Ρ indicates that three propylene units are continuous, and ΕΕΕ indicates that three ethylene units are continuous. Table 1 Assignment table (ppm)

note)

Chemical shift criteria

The peak top of S <5 <5 was set to 30.01 ppm

The ethylene unit content ( _α (weight)) in the propylene random copolymer was calculated from each signal intensity according to the following equation.

α = 2 (300— X)

X = E t / S X 1 00

E t = I EEE +2/3 (I PEE + I EPE) +1/3 (I PPE + I PEP) S = I EPE + I PPE + IEEE + 1 PPP + I PEE + I PEP

I EPE = I (4) I PPP = 1 (8)

I PPE = I (5) I PEE = I (9)

I EEE = I (7) / 2 + I (6) / AI PEP = I (10) Here, for example, 1 (1) is the signal intensity of signal number 1 in Table 1.

The stereoregularity index (P (mol%)) was calculated from the following equation.

P = I (11) / (I (11) + I (12) + I (13)-I (4)-I (5)) X 100 This P value is the value of the triac in the propylene chain region of the copolymer molecular chain. It is an isotactic fraction in C units. In this equation, the signal intensity of the methyl carbon of the propylene unit at the center of the PPE chain appearing in the mr region is determined by the signal intensity of Tj3S (No. 5 signal) of the propylene unit in the EPE chain appearing in the rr region. The signal intensity of methyl carbon is substituted by the signal intensity of Τ δ δ (4th signal).

②Temperature Separation Chromatograph (TREF)

The sample solution is introduced into the TREF column adjusted to a temperature of 135, and then the temperature is gradually decreased to 0 at a rate of 5 Ζΐr to allow the sample to be adsorbed on the packing material. Thereafter, the temperature of the column was increased to 135¾ at a speed of 4 Othr, and an elution curve was obtained. The temperature at which the elution amount shows a peak was defined as Tp. Wp and W0 were determined from the obtained elution curves.

The measurement equipment and measurement conditions are shown below.

1) Measuring device

TREF column:

GL Science's silica gel column (4.60 x 150 mm) Flow Senole: GL Science's optical path length 1 mm KB r Senole Liquid sending pump: SSC-3100 pump from Senshuu Kagaku

Vanolev oven: GL Science MODEL 554 oven

TREF oven: GL Science

Two-series temperature controller: REX-C 100 temperature controller manufactured by Rigaku Corporation

Detector: Infrared detector for liquid chromatography FOXBORO MI RAN 1 A CVF

10-way valve: Electric valve manufactured by PARCO

Loop: Parco 500 liter loop

2) Measurement conditions

Solvent: Norebenzene

Sample concentration: 7.5 gZ liter

Injection volume: 500 μl

Pump flow rate: 2.0 milliliter / min

Detection wave number: 3.41 μπι

Column packing material: Chromosolve Ρ (30-60 mesh)

Column temperature distribution: within ± 2.0

③ Intrinsic viscosity [7J]

135 was measured in a tetralin solvent.

[7J] Β of the polymer [Β] was calculated by the following formula.

[7J] _B = ([7J] _H — [7j] _A XW _A ) Z (1— W _A )

However,

The intrinsic viscosity [7J] A of the polymer [A] was measured on a sampled sample as described above. The weight fraction W _A of the polymer [A] was calculated from the yield. The weight fraction (11 W _A ) of the polymer [B] was calculated from the yield. The intrinsic viscosity of the propylene block copolymer [77] The final product was measured as described above.

"Film quality evaluation method _)

Film formation and films line Le a Aniru processing all temperatures 4 at 24 hours ,, further temperature 23 ± 2 ^c t, 16 hours or more conditioned at humidity 50 ± 10% After that, measurement was performed under the same temperature and humidity conditions.

① Transparency (haze)

The measurement was performed according to JIS K 7105.

② Impact resistance

It was evaluated by the impact fracture strength using a 1/2 inch impact head with a film impact tester manufactured by Toyo Seiki Seisakusho. The results are shown as 〇 for excellent, △ for normal, and X for poor.

③ Tensile modulus

It was measured under the following conditions by a tensile test according to JIS K 712.

Crosshead speed: 500 mm / min

Load cell: 10 kg

Measuring direction: Machine direction (MD)

Sticky

It was evaluated by touch. The results indicate that 〇 is excellent, Δ is normal, and X is poor.

(Examples 1 to 5)

(Adjustment of solid catalyst components)

To a 3-necked flask equipped with a stirrer having an internal volume of 5 L and purged with nitrogen, 160 g of diethoxymagnesium was charged, and 600 ml of dehydrated octane was further added. The mixture was heated to 40, 24 ml of silicon tetrachloride was added, the mixture was stirred for 20 minutes, and 16 ml of dibutyl phthalate was added. The temperature of the solution was raised to 80, and 77 O ml of titanium tetrachloride was subsequently added dropwise using a dropping funnel. The internal temperature was set to 1 251 and the reaction was carried out for 2 hours. Thereafter, washing was performed sufficiently using 125 dehydrated octane. Further, 122 Om1 of titanium tetrachloride was added, the internal temperature was set to 1251, and a contact reaction was performed for 2 hours. Then add 1 2 5 脱水 of dehydrated octane After washing sufficiently, a solid component [A] was obtained.

(Preliminary polymerization)

48 g of the solid component [A] was charged into a 1-L three-necked flask equipped with a stirrer and purged with nitrogen, and 40 Oml of dehydrated heptane was added. The mixture was heated to 40 and 5.9 ml of triethylaluminum 2.Om 1 and isobutyl mono-n-butylpyrumethoxysilane were added. Propylene was allowed to flow at normal pressure and reacted for 2 hours. Thereafter, the catalyst was sufficiently washed with dehydrated octane to obtain a catalyst component.

(Production of propylene block copolymer)

30 g of a poly (propylene ethylene random copolymer) powder was charged into a 5-liter stainless steel autoclave with a stirrer, and the system was sufficiently purged with nitrogen gas. 2.0 mmol of triethylaluminum, dicyclopentyldimethoxysilane 0.5 mmol and 0.01 mmol of the above-mentioned solid catalyst component in terms of titanium atoms were charged, and hydrogen was fed at 1.0 kg / cm ² G, and ethylene and propylene at a volume ratio shown in Table 2, and the total pressure was increased. Was adjusted to 15.O _kg cm ² G, and polymerization was performed at 7 for 60 minutes to produce a propylene copolymer [A]. Subsequently, after purging the reaction gas in the system, [7]] sampling for measurement was performed, and hydrogen 1.O kgZcm ² G and ethylene and propylene were fed at the volume ratio shown in Table 2, The propylene copolymer [B] was produced by adjusting the polymerization time so that the copolymerization ratio shown in Table 2 was obtained at 70 at a pressure of 15.O kg cm ² G, and the propylene block copolymerization was performed. A coalescence was obtained. The measurement was performed according to the above-mentioned “Resin Characteristic Evaluation Method”. The obtained polypropylene copolymer was pelletized with a 2 Omm0 extruder, and then a CPP film was formed at 2 Omm °. The measurement was performed according to the above-mentioned “Evaluation method of film quality”. Tables 2 and 3 show the obtained results. (Comparative Examples 1 to 3) (Adjustment of solid catalyst components)

Into a three-neck flask with a stirrer having a volume of 5 L and purged with nitrogen, 160 g of diethoxymagnesium was charged, and 6 Oml of dehydrated heptane was added. The mixture was heated to 40, 24 ml of silicon tetrachloride was added, the mixture was stirred for 20 minutes, and 25 ml of dimethyl phthalate was added. The temperature of the solution was raised to 80, and 47 Oml of titanium tetrachloride was subsequently added dropwise using a dropping funnel. The internal temperature was set at 110 t and the reaction was carried out for 2 hours. Thereafter, washing was carried out sufficiently using 90 dehydrated heptane. Furthermore, 77 Oml of titanium tetrachloride was added, the internal temperature was adjusted to 110, and a contact reaction was performed for 2 hours. Thereafter, washing with water was carried out using 9 dehydrated heptane to obtain a solid component [B].

(Preliminary polymerization)

48 g of the solid component [B] was charged into a 1 L three-necked flask equipped with a stirrer and purged with nitrogen, and 40 Om 1 of dehydrated heptane was added. The mixture was heated to 10 and 2.7 ml of triethylaluminum and 2.Oml of hexylmethyldimethoxysilane were added. Propylene was allowed to flow through the mixture at normal pressure to react for 2 hours. Thereafter, the catalyst was sufficiently washed with dehydrated heptane to obtain a catalyst component.

(Production of propylene block copolymer)

30 Into a 5-liter stainless steel autoclave equipped with a stirrer, 30 g of a poly (propylene ethylene random copolymer) was charged, and the system was sufficiently purged with nitrogen gas. Then, 2.0 mmol of triethylaluminum, dicyclopentyldimethoxysilane 0 .5 mmol and 0.01 mmol of the above solid catalyst component in terms of titanium atom were charged, and ethylene and propylene were fed at the volume ratio shown in Table 4, and the total pressure was adjusted to 15.0 kg / cm ² G, Polymerization was carried out at 7 for 60 minutes to produce a propylene copolymer [A]. After purging the reaction gas in the system, [7J] 1.0 kg / cm ² G of hydrogen and ethylene and propylene were fed at the volume ratios shown in Table 4, and the total pressure was set to 15.OkgZcm ² G. A propylene copolymer [B] was produced by adjusting the polymerization time so that the copolymerization ratio was obtained, and a propylene block copolymer was obtained. The measurement was performed according to the above-mentioned “Resin Characteristic Evaluation Method”.

The obtained polypropylene copolymer was pelletized with a 20 mm0 extruder, and subsequently, a CPP film was formed at 2 mm0. The measurement was performed according to the above-mentioned “Evaluation method of film quality”. Tables 4 and 5 show the obtained results. [Comparative Examples 4, 5]

(Production of propylene block copolymer)

30 g of polypropylene powder was charged into a 5-liter stainless steel autoclave with a stirrer, and the system was sufficiently purged with nitrogen gas. 2.0 mmol of triethyl aluminum and 0.5 mmol of dicyclopentyldimethoxysilane And 0.01 mmol of the same solid catalyst component as in Comparative Examples 1 and 2 were added in terms of titanium atoms, 5.0 kg of Zcm ² G of hydrogen and 23.0 kg / cm ² G of propylene were introduced, and the total pressure was 28 Polymerization was performed at O _kg / cm ² G, 7 for 45 minutes to produce a propylene homopolymer. Subsequently, after purging the reaction gas in the system, sampling for [7J] measurement was performed, hydrogen 3.0 kg Zcm ² G and ethylene and propylene were fed at the volume ratios shown in Table 4, and the total pressure was reduced. 15.0 kg / cm ² G, propylene block [B] was produced by adjusting the polymerization time at 70 °: so that the copolymerization ratio shown in Table 4 was obtained, and propylene block copolymerization was performed. A coalescence was obtained. The measurement was performed according to the above-mentioned “Resin Characteristic Evaluation Method”.

The obtained polypropylene copolymer was pelletized with a 20 mm 0 extruder, and then a CPP film was formed at 2 mm 0. The measurement was performed according to the above-mentioned “Evaluation method of film quality”. Tables 4 and 5 show the obtained results. (Comparative Example 6)

(Production of propylene random copolymer)

30 g of a polypropylene-ethylene random copolymer powder was charged into a 5-liter stainless steel autoclave equipped with a stirrer, and the system was sufficiently purged with nitrogen gas. Then, 2.0 mmol of triethylaluminum, dicyclopentyldimethyl 0.5 mmol of toxicoxysilane and 0.01 mmol of the same solid catalyst component as in Example 1 were added in terms of titanium atom, and hydrogen was fed at 0 kg / cm ² G and ethylene and propylene at the volume ratios shown in Table 4. Then, polymerization was performed for 60 minutes at a total pressure of 1.5 kg OgZcm ² G and 7, thereby producing a propylene copolymer [A]. The measurement was performed according to the above-mentioned “Resin Characteristic Evaluation Method”.

The obtained polypropylene copolymer was pelletized with a 20 mm φ extruder, and then a CPP film was formed at 2 nm. The measurement was performed according to the above-mentioned “Evaluation method of film quality”. Tables 4 and 5 show the obtained results.

Table 2

Wei Example 2 Departure 3 Example 4 Phaze (%) 2.3 6 2.2 1.6 1.4

Leaf drawing rate (IVPa) 419 383 316 254 218

生〇〇繊繊

Sticky 〇〇〇〇〇 Table 4

ί 瞧 1 i relation 2 Female example 3 4 J ^ Example 5 J ^ Example 6 Water (kg / cm ² G)

Comonomer Ethylene Ethylene Ethylene Ethylene Ethylene Fiber (vol |) | 10/1 7/1 12/1 12/1 (Buylene / I-Tylene)

Dl / g) 1.24 1.61 1.89 1.3 1.3 1.92

I-Tylene content (wt%) 6.5 9.4 4.3 4.0 ()

Wp (wt¾) 25.3 12.5 49.8 53.1

WO (wt¾) 4.2 2.35 2.18

(3+ la ヽ I 5.45 2.9 2.75 Polymer ratio (wt¾!) 50 44.4 63.4 62 21

Mizunen (kg / cm ² G)

Comonomer I-Tylene I-Tylene I-Tylene I-Tylene I-Tylene

Fu Hiroto 'Riki' Susen (vol 50 I 4/1 | 1/1 I 2/1 I 7/3 | 7/3

(P. Vino / 1 Tylene)

["] (dl / g) 2.24 3.15 2.74 1. 1.

I-Tylene content (wt¾l) 21.9 40.4 21.2 24 25

LT3 〇

, »

寸 dimensions

C

〇 X

One-ws

〇 X

CO

<X

Π5

Industrial applications

The propylene block copolymer of the present invention has an excellent balance of transparency, room temperature impact, low temperature impact, flexibility and blocking properties, and can be suitably used for films, sheets or the like.

Claims

The scope of the claims

1. the following (1) to propylene one ethylene copolymer satisfying (3) [A] 50 to 90 weight ⁰ / o and having an ethylene content of 10 to 25 weight ^_0/0 propylene Nechiren copolymer [B] A propylene-based copolymer comprising 10 to 50% by weight of ⁰ / o.

(1) The ethylene content (α) measured by ¹³ C-NMR is 0.2 to 10% by weight

(2) Assuming that the main elution peak temperature of the temperature rising fractionation chromatograph is Τρ (¾), the amount of the component (Wp) eluted in the temperature range of (Τρ-5) 〜: to (〜ρ + 5) is 20% by weight. Is over

(3) Satisfies the relationship between the amount of component eluted (W0) and α force; and W0 ≤ (3 + 2α) 4 in the temperature range of 0 or less in the temperature rising fractionation chromatograph.

3. Propylene satisfy (1) to (3) below - ethylene copolymer [Alpha] 50 to 85 weight ^_0/0 and propylene Len one ethylene copolymer having an ethylene content of 10 to 25 weight ⁰ / o [ Β] The propylene-based copolymer according to 1 or 2 above, comprising 15 to 50% by weight.

(1) The ethylene content (α) measured by ¹³ C-NMR is 0.5 to 9% by weight

(2) Assuming that the main elution peak temperature of the temperature rising fractionation chromatograph is Tp i), the component (Wp) eluted in the temperature range of (Tp-5): to (Tp + 5) t is 20% by weight or more. Is

(3) Elution is performed in the following temperature range of the fractionated chromatograph Satisfies the relationship between component amount (WO) and α force WO ≤ (3 + 2α) 4

4. Any one of the above items 1 to 3, wherein the component amount (β) (% by weight) and tensile modulus (ΤΜ) (unit: MPa) of the above-mentioned propylene-based copolymer satisfy the following relationship. Propylene copolymer.

TM <2 X 10 ⁵ X (β) ^{1 7}

5. The propylene block copolymerization method in the above 2 comprises (Α) a solid catalyst component obtained by contacting and reacting a magnesium compound, a titanium compound, and an electron donating compound, (Β) an organoaluminum compound, and (C) ) The following general formula (I)

S i R ¹ 2 (OR ² ) 2

(In the formula, R ¹ represents a branched chain hydrocarbon group having 1 to 20 carbon atoms or a saturated cyclic hydrocarbon group, and R ² represents a straight chain hydrocarbon group having 1 to 4 carbon atoms or a branched chain group. Which may be the same or different from each other.) A method for producing propylene and ethylene in a multistage polymerization in the presence of a catalyst comprising an organic silicon compound represented by the formula: 5. The propylene-based copolymer according to any one of the above 2 to 4.

6. The propylene block copolymerization method in (2) above: (A) Contact at a temperature of 12 to 150 ° C in the presence of a magnesium compound, a titanium compound, an electron-donating compound and, if necessary, a silicon compound. After that, a solid catalyst component obtained by washing with an inert solvent at a temperature of 10 or more and 15 or less, (B) an organoaluminum compound, and if necessary, (C) an electron-donating component as a third component. 5. The propylene-based copolymer according to any one of the above items 2 to 4, which is a production method in which propylene and ethylene are subjected to multistage polymerization in the presence of a catalyst comprising a compound.

7. A composition comprising the propylene-based copolymer described in any of the above 1 to 4. oi OAV ps / 一

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